CN113512050A - Cuprous iodide complex-based pyridine VOC (volatile organic Compounds) fluorescent sensing material - Google Patents
Cuprous iodide complex-based pyridine VOC (volatile organic Compounds) fluorescent sensing material Download PDFInfo
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- 229910021595 Copper(I) iodide Inorganic materials 0.000 title claims abstract description 106
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 title claims abstract description 54
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011540 sensing material Substances 0.000 title claims description 23
- 239000012855 volatile organic compound Substances 0.000 title abstract description 55
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 104
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 56
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- 239000010408 film Substances 0.000 description 27
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 19
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
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- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
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Abstract
The invention discloses a cuprous iodide complex luminescent material, a preparation method thereof and a sensing application of the material to pyridine VOC (volatile organic compounds); the structural formula of the luminescent material is CuI (TPP)2(TU), wherein TPP is triphenylphosphine and TU is thiourea; prepared by sequentially carrying out coordination reaction on CuI and a ligand; the material has weak luminous intensity, but after being placed in pyridine or picoline atmosphere, the material quickly shows a lighted fluorescence sensing response characteristic; the material is easy to prepare, has good solubility and stability, is also easy to prepare a paper-based supported or polymer-doped fluorescent sensing film, and rapidly shows fluorescence lighting capable of being observed by naked eyes in an atmosphere containing pyridine or p-picolineThe test paper can be flexibly manufactured into various required specifications, and can be used as a portable fluorescence sensing test paper device for detecting the pyridine VOC.
Description
Technical Field
The invention relates to the technical field of luminescent materials, relates to the field of photoluminescence materials, and particularly relates to the field of fluorescence sensing materials.
Background
Volatile Organic Compounds (VOC) are abbreviated as VOC. Volatile organic substances are numerous, unstable and ubiquitous. They include chemical compounds that are man-made and naturally occurring. Most Volatile Organic Compounds (VOCs) are transmitted as a vapor. In China and many countries around the world, the artificial emission of VOC is subject to legal sanctions. While harmful VOCs are generally not acutely toxic, exposure to VOCs at different concentrations can have health effects to varying degrees over an extended period of time. However, since the concentration of VOCs in the environment is generally low and the symptoms often develop slowly and inconspicuously, there are difficulties and inconveniences with the current research on VOCs and their effects.
However, with the rapid development of national economy, situations involving the utilization or emission of VOCs in various industries, such as petrochemical industry, decoration industry, etc., are ubiquitous, which causes many problems of air pollution. For example, various organic/polymeric building and finishing materials, which are used in large quantities in the housing industry, have raised problems of indoor air pollution, and these problems have also been receiving much attention. In fact, VOC is a main factor of indoor air pollution, and its specific components include benzene series, organic chloride, freon series, pyridine compounds, etc., and its sources are mainly coatings, wall papers, floor tiles, heat insulating materials, adhesives, etc. in the aspects of interior decoration materials and furniture. To understand the VOC condition in the air, it is important to detect/detect it. The existing methods comprise the following steps: gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), membrane techniques for volatile organic compounds, instrumental VOC determination, chemical analysis of volatile organic compounds, and the like. However, these methods have certain shortcomings, such as difficulty in miniaturization of the instrument, difficulty in carrying, complicated detection procedures, high cost, too long detection time, sample consumption in detection, secondary emission pollution generation, and the like.
Compared with the traditional detection method, the fluorescence sensing detection method is increasingly paid attention, and research and development forces are continuously invested. Because the fluorescence sensor has the advantages of high sensitivity, abundant collected signals, easy miniaturization of the instrument, no loss of samples, convenient use and the like, the development of the fluorescence sensor is steadily promoted towards the direction of comprehensive practicability. Fluorescence sensors are mainly classified into two categories: thin film fluorescence sensors that are easy to reuse and are capable of sensing responses to gas phase substances, and homogeneous fluorescence sensors for use in solution. The main structure of a fluorescence sensor is generally composed of three parts: a receptacle for foreign material, a reporter, and a connector. The role of the receptor is apparent throughout the fluorescent sensor structure, which is responsible for the reception of foreign molecules, the conversion of the signal. The choice of the receiver material (i.e. the sensitive material) and the preparation process are therefore of crucial importance, which directly determines the performance and range of applications of the sensor.
The existing luminescent materials are biological, inorganic and organic materials, and have advantages and disadvantages respectively. Biological materials have a very high position in the field of biological monitoring, but have relatively large limitations in other fields. Inorganic materials have good space for pressure and temperature sensing due to their physical properties, but have problems in gas and water source detection. The reason is that although inorganic powder has good stability, since its internal structure is too dense and its luminescence center is hardly influenced by external atmosphere, only a few small molecule sensors such as oxygen have been reported (Sensors And Actuators B-Chemical 2018,254578- & ltSUB & gt 587.), but fluorescence sensing for VOCs has not been seen. The organic molecules (pure organic materials) have various structures and properties, are convenient to design and optimize, and have some reports of VOC fluorescence sensing at present. For example, the sensing detection of electron-deficient nitrobenzene explosives is reported in 2007 by the fluorescence quenching mechanism based on intermolecular Charge Transfer (CT), Zhang L.equals to the university of Utah, and the fluorescent material is a p-type organic semiconductor (Journal of the American Chemical Society 2007,129(22), 6978-6979.). However, the fluorescence of organic materials is greatly affected by molecular packing, and aggregation-induced fluorescence quenching (ACQ) is the most prominent phenomenon. In general, the development of organic materials is still limited by the existence of problems such as stability and reliability.
According to a large number of existing research reports, the complex can form a hybrid material with good stability through coordination hybridization of inorganic and organic materials, and can show a fluorescence sensing function, so that the complex is a good organic combination inorganic material and organic materialThe solution of the material advantage. Wenger reviewed the vaporomism of complexes and their VOC sensing application prospects, predicting that this is a simple and inexpensive solution (Chemical Reviews 2013,113(5), 3686-3733). However, as mentioned herein, researchers in this area are currently generally studying only the molecular mechanisms of this phenomenon, and neglect the application requirements of quantitative, inexpensive, etc. of practical sensing. Particularly, the platinum and gold used in the complex reported at present are expensive, and the low-cost requirement of the application is met. Compared with other metals, copper has the advantages of low price, environmental protection, no toxicity and the like, and the copper resource reserves of China are abundant and third place in the world. However, it is reported from the existing research at present that the cuprous complex is not only based on cheap metal, but also has good luminescent properties, and the luminescent properties (such as the regulation of luminescent wavelength and quantum yield) can be regulated and controlled by the structure, so that the cuprous complex can be surmised to be a promising molecular development platform for VOC fluorescence sensing detection. The key problem at present is to find/develop a cuprous complex sensing material with VOC fluorescent response performance, thereby promoting the wide application of the VOC fluorescent sensing technology.
Disclosure of Invention
The invention aims to provide a novel cuprous iodide complex luminescent material, a preparation method thereof and a sensing application of the material to pyridine VOC. The cuprous iodide complex luminescent material with good thermal stability is conveniently and cheaply prepared by the stepwise coordination reaction of cuprous iodide and two ligand solutions, and is found to have reversible and selective fluorescent response to pyridine and picoline in various VOC atmospheres, and the original weak luminescence is changed into strong fluorescence.
One of the technical schemes of the invention is to provide a novel cuprous iodide complex luminescent material, which is obtained by sequentially carrying out coordination reaction on CuI, ligand triphenylphosphine and thiourea, and has a molecular structure of CuI (TPP)2(TU), wherein TPP is electrically neutral monophosphine ligand triphenylphosphine, and TU is sulfur-containing ligand thiourea.
The cuprous iodide complex luminescent materialIs a triclinic system, P-1 space group, and has unit cell parameters a =9.7713(3), b =11.8827(4), c =16.0872(6) a, α =85.1850(10) ° β =80.3690(10) ° γ =69.6340(10) ° V =1725.76(10) a3 , Z=2，DC=1.534 g/cm3 The crystal color of the material is light yellow and nearly colorless; the structure of the material is represented as a mononuclear neutral complex, wherein the cuprous ions adopt CuIP2(ii) S tetrahedral coordination mode, wherein one I is iodide, two P are from two phosphine ligands triphenylphosphine, and one S is from one thio-containing ligand thiourea, respectively; the molecular structure is shown as formula (I):
the cuprous iodide complex luminescent material emits weak fluorescence under the excitation of ultraviolet light, and is difficult to observe by naked eyes; after the sensor is placed in a pyridine VOC steam environment, the sensor can quickly show a similar lighting luminous effect, and therefore, the sensor can be used as a sensing material for detecting the pyridine VOC.
The second technical proposal of the invention is to provide a cuprous iodide complex luminescent material CuI (TPP)2A preparation method of (TU). The preparation method is realized by mixing CuI with acetonitrile solutions of ligands TPP and TU to perform a coordination reaction, and finally separating out a product of crystal powder. The specific implementation scheme comprises five steps:
(1) dissolving CuI powder in acetonitrile at room temperature;
(2) dissolving TPP powder in acetonitrile at room temperature;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) dissolving TU powder in acetonitrile at room temperature, adding into the solution A, mixing and stirring to fully perform coordination reaction to obtain a solution B;
(5) filtering the obtained solution B, performing reduced pressure rotary evaporation at room temperature, and drying to obtain crystal powder, namely a target product; the molar ratio CuI to TPP to TU of the three reactants is 1: 2: 1.
In the third technical scheme of the invention,provides a luminescent material CuI (TPP) based on a cuprous iodide complex2(TU) a method for preparing a paper-based fluorescent sensing film. The preparation method is that the cuprous iodide complex CuI (TPP)2(TU) after dissolution, the solution was applied to a cellulose film. The specific implementation scheme comprises four steps:
(1) reaction of cuprous iodide Complex CuI (TPP) at room temperature2(TU) the powder was dissolved in acetonitrile;
(2) manufacturing a cellulose film into a shape which is required to be conveniently applied to form test paper base paper;
(3) mixing the above complex CuI (TPP) at room temperature2(TU) coating the solution on test paper base paper;
(4) and finally, drying the coated test paper under a vacuum condition, and obtaining the sensing film after drying.
The fourth technical scheme of the invention is to provide a cuprous iodide complex luminescent material CuI (TPP)2(TU) a method for preparing a doped fluorescent sensing film. Copper iodide complex CuI (TPP)2The (TU) is embedded in PMMA (polymethyl methacrylate) to realize, and the specific embodiment thereof is divided into four steps:
(1) dissolving PMMA solid in dichloromethane at room temperature;
(2) reaction of cuprous iodide Complex CuI (TPP) at room temperature2(TU) the powder was dissolved in acetonitrile;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) and spin-coating the clear solution A on a quartz plate at room temperature, and drying to obtain the sensing film.
The fifth technical scheme of the invention is to provide a cuprous iodide complex luminescent material CuI (TPP)2(TU) and its base paper sensing film's selective fluorescence sensing performance to pyridine VOC vapour. Supported cuprous iodide complex CuI (TPP) with originally weak luminescence2After the test paper of (TU) responded in the atmosphere of pyridine and 4-methylpyridine, very bright blue-green luminescence (emission peak wavelengths of about lambda respectively) was rapidly observedem= 505 nm and 490 nm). In addition to that, in othersIn the VOC atmosphere, it still emits light so weakly as to be difficult to distinguish with the naked eye. The presence of a variety of other VOC vapors does not have an observable effect on the fluorescence sensing performance of pyridine and picoline vapors. These phenomena indicate that the cuprous iodide complex luminescent material has fluorescence sensing properties that are selectively responsive to specific VOCs (pyridine and p-picoline vapor).
The sixth technical scheme of the invention is to provide a cuprous iodide complex luminescent material CuI (TPP)2(TU) and its polymer doped sensing film's selective fluorescence sensing performance on pyridine VOC vapors. Polymer doped cuprous iodide complex CuI (TPP) with weak original luminescence2After The (TU) film responded in the atmosphere of pyridine and 4-methylpyridine, very bright blue-green luminescence (emission peak wavelengths of about lambda each) was rapidly observedem= 505 nm and 490 nm). In addition, in other VOC atmospheres, it still emits so little light that it is difficult to distinguish with the naked eye. The presence of a variety of other VOC vapors does not have an observable effect on the fluorescence sensing performance of pyridine and picoline vapors. These phenomena indicate that the cuprous iodide complex luminescent material has fluorescence sensing properties that are selectively responsive to specific VOCs (pyridine and p-picoline vapor).
The invention has the beneficial effects that firstly, the cuprous iodide complex luminescent material CuI (TPP) is provided2(TU), the complex material has the advantages of low price and easy purification, and has good solubility and thermal stability, so that technical support is provided for further application of the material, and due to the existence of the terminal ligand phosphine ligand TPP and the sulfur-containing ligand TU, a proper space and intermolecular interaction mode is provided in the molecular structure, and a foundation is provided for subsequent sensing performance research.
The invention has the beneficial effects that the cuprous iodide complex luminescent material CuI (TPP)2(TU) fluorescence sensing application with selective response to pyridine and 4-methylpyridine, wherein the response can be rapidly completed in a short time, the fluorescence performance of the complex material after response is good, and a very small amount of material powder can emit strong fluorescence, so that only a small amount of fluorescence is needed in practical applicationThe optical powder is convenient for reducing the application cost, and the doping way which is easy to operate also provides convenience for controlling the application cost; after the material prepared by the same process is placed in pyridine or picoline atmosphere, the fluorescent lighting sensing response characteristic can be quickly observed; and the solubility, the stability and the reversible response performance of the fluorescent sensing material are good, so that the fluorescent sensing material is convenient to use.
The invention has the beneficial effects that the cuprous iodide complex-based luminescent material CuI (TPP)2(TU) the use of the paper-based fluorescent film is as simple as that of a common gas detection test paper, and in particular, when the paper-based fluorescent film is used, the paper-based fluorescent film is placed in an environment existing in pyridine or picoline atmosphere for a short time and then is irradiated by an ultraviolet light source, so that the appearance of rapid fluorescence lightening can be observed, the VOC concentration is increased, the fluorescence response effect of strength enhancement is shown, and the fluorescence sensing performance of reversible quick response and sensitive identification is shown, so that the paper-based fluorescent film can be used as a portable fluorescence sensing test paper device to be used for detecting the pyridine VOC; the fluorescent sensing film can be flexibly manufactured into various required shapes, has light weight, is very convenient to carry and easy to prepare, and provides technical support for further application of luminescent materials.
The invention has the beneficial effects that finally, the cuprous iodide complex luminescent material CuI (TPP) is prepared2The (TU) and the method for preparing the sensing film have the advantages of simple and convenient process, simple used equipment, simple and easily obtained raw materials, low production cost, high material preparation yield, capability of obtaining a large amount of products in a short time, easiness in popularization and the like.
Drawings
FIG. 1. cuprous iodide Complex luminescent Material CuI (TPP)2Single crystal structure of (TU) molecule.
FIG. 2. cuprous iodide Complex luminescent Material CuI (TPP)2(TU) stacking patterns of molecules within the unit cell and in the surrounding space.
FIG. 3. cuprous iodide Complex luminescent Material CuI (TPP)2(TU) X-ray powder diffraction pattern: (a) obtained for calculation simulation of data of a single crystal structure according to example 2(ii) a spectrum; (b) is a spectrum of the powder obtained in example 1 of the present invention.
FIG. 4. cuprous iodide Complex luminescent Material CuI (TPP)2Infrared absorption (FTIR) spectrum of (TU).
FIG. 5. cuprous iodide Complex luminescent Material CuI (TPP)2Ultraviolet-visible absorption (UV-Vis) spectrum of (TU).
FIG. 6. cuprous iodide Complex luminescent Material CuI (TPP)2(TU) fluorescence (PL) spectrum, excitation spectrum on the left and emission spectrum on the right.
FIG. 7 shows a load CuI (TPP)2(TU) fluorescence emission spectra of the paper-based film before and after response in pyridine atmosphere for a certain time.
FIG. 8 shows a load CuI (TPP)2Fluorescence emission spectra of the paper-based films of (TU) before and after response in a 4-picoline atmosphere.
FIG. 9 Polymer-based doped CuI (TPP)2(TU) fluorescence emission intensity change spectrogram after response for a certain time in pyridine atmosphere.
FIG. 10 Polymer-based doped CuI (TPP)2Fluorescence emission spectra of The (TU) fluorescence sensing film before and after response in 4-methylpyridine atmosphere for a certain time.
Detailed Description
The implementation process and the performance of the material of the invention are illustrated by the examples:
example 1
A large number of cuprous iodide complex luminescent materials CuI (TPP)2(TU) preparation of crystalline powder samples: weigh 0.038g (0.2 mmol) of CuI, 0.105g (0.4 mmol) of Triphenylphosphine (TPP), 0.016g (0.2 mmol) of Thiourea (TU); dissolving the raw materials respectively with 10mL of acetonitrile, then sequentially mixing, and fully stirring to enable the raw materials to fully generate coordination reaction to obtain a light yellow clear solution; after filtration, the solution was rotary evaporated under reduced pressure to remove all solvents and dried to give the product as a pale crystalline powder with a yield of 91% (calculated as Cu). Placing the complex luminescent material in pyridine and 4-methylVery bright fluorescence emission was rapidly observed after response in pyridine atmosphere.
Example 2
Synthesis of cuprous iodide Complex phosphor CuI (TPP)2Single crystal of (TU): weigh 0.038g (0.2 mmol) of CuI, 0.105g (0.4 mmol) of Triphenylphosphine (TPP), 0.016g (0.2 mmol) of Thiourea (TU); dissolving the raw materials respectively with 10mL of acetonitrile, then sequentially mixing, and fully stirring to enable the raw materials to fully generate coordination reaction to obtain a light yellow clear solution; after filtering, carrying out rotary evaporation on the solution under a reduced pressure condition to remove all solvents, and drying to finally obtain light-colored crystal powder; then the obtained crystal powder is redissolved by using a proper amount of hot acetonitrile and filtered while the crystal powder is hot, and a large amount of almost colorless massive crystals are separated out after the filtrate is stood. One nearly colorless bulk crystal of 0.38mm by 0.23mm by 0.18mm size was picked for X-ray single crystal structure testing. The molecular structure diagram of the compound is shown in figure 1, and the unit cell stacking structure diagram is shown in figure 2.
Example 3
Supported CuI (TPP)2Preparation of fluorescent sensing film of (TU) and its atmosphere response: 0.040g of cuprous iodide complex luminescent material CuI (TPP) is weighed2(TU) to dissolve completely in 7 mL acetonitrile, the solution was pale yellow, clear and transparent, and filtered. The cellulose film is made into a size and a shape suitable for application by methods such as cutting and the like and is used as test paper base paper used in the subsequent process; taking a proper amount of filtrate, and coating the filtrate on the test paper base paper by using a printing, dip-coating or brush-coating method; drying the coated test paper under vacuum condition (60 ℃, 30 min), and obtaining a fluorescent sensing film (fluorescent test paper) after drying is finished; the sensing film is then placed in the VOC to respond and the fluorescence spectrum is tested. It was found that very bright fluorescence emission was observed after response in an atmosphere of pyridine and p-picoline. In addition, in other VOC atmospheres, it still emits light weakly and is difficult to distinguish with the naked eye. The presence of a variety of other VOC vapors does not significantly affect the fluorescence sensing performance of pyridine and picoline vapors. These phenomena indicate that the cuprous iodide complex material has selective response to sensing of specific VOCs (pyridine and p-picoline vapors)Energy (see fig. 7 and 8).
Example 4
Supported CuI (TPP)2Preparation of fluorescent sensing film of (TU) and its atmosphere response: weighing 0.080g of cuprous iodide complex luminescent material CuI (TPP)2(TU) to dissolve completely in 10mL tetrahydrofuran, the solution was pale yellow, clear and transparent, and filtered. The cellulose film is made into a size and a shape suitable for application by methods such as cutting and the like and is used as test paper base paper used in the subsequent process; taking a proper amount of filtrate, and coating the filtrate on the test paper base paper by a micro-spraying, dip-coating or spot-coating method; drying the coated test paper under vacuum condition (60 ℃, 30 min), and obtaining a fluorescent sensing film (fluorescent test paper) after drying is finished; the sensing film is then placed in the VOC to respond and the fluorescence spectrum is tested. It was found that very bright fluorescence emission was observed after response in an atmosphere of pyridine and p-picoline. In addition, in other VOC atmospheres, it still emits light weakly and is difficult to distinguish with the naked eye. The presence of a variety of other VOC vapors does not significantly affect the fluorescence sensing performance of pyridine and picoline vapors. These phenomena indicate that the cuprous iodide complex material has selective response sensing performance for specific VOCs (pyridine and p-picoline vapor) (see fig. 7, fig. 8).
Example 5
Polymer-based doped cui (tpp)2Preparation of fluorescent sensing film of (TU) and its atmosphere response: 0.5g of PMMA (polymethyl methacrylate, glass transition temperature: 105 ℃) was weighed out and dissolved completely in 10mL of methylene chloride, and the solution was colorless, clear and transparent. 0.080g of cuprous iodide complex luminescent material CuI (TPP)2(TU) to dissolve completely in 10mL acetonitrile, the solution was pale yellow, clear and transparent. The complex solution is slowly introduced into the PMMA solution, and the solution is light in color, clear and transparent. Spin-coated (1200 rad/min) on cleaned quartz plates, dried (60 ℃, 30 min), and then placed in VOC for response to test the fluorescence spectra. As a result, it was found that very bright luminescence was observed after the response in the atmosphere of pyridine and 4-methylpyridine. In addition, in other VOC atmospheres, it still emits light weakly and is difficult to distinguish with the naked eye.The presence of a variety of other VOC vapors does not significantly affect the fluorescence sensing performance of pyridine and picoline vapors. These phenomena indicate that the cuprous iodide complex material has selective response sensing performance for specific VOCs (pyridine and p-picoline vapor) (see fig. 9, fig. 10).
Claims (6)
1. A cuprous iodide complex fluorescence sensing material is characterized in that: the structural formula of the fluorescent sensing material is CuI (TPP)2(TU), wherein TPP is an electric neutral monophosphine ligand triphenylphosphine, and TU is a sulfur-containing ligand thiourea; the cuprous iodide complex fluorescent sensing material is a triclinic system, a P-1 space group, unit cell parameters a =9.7713(3) a, b =11.8827(4) a, c =16.0872(6) a, α =85.1850(10) °, β =80.3690(10) °, γ =69.6340(10) °, V =1725.76(10) a 3, Z =2, DC =1.534 g/cm3, and the crystal color of the material is light yellow and colorless; the structure of the material is represented as a mononuclear neutral complex, wherein cuprous ions adopt a CuIP2S tetrahedral coordination mode, wherein one I is iodide, two P are respectively from two phosphine ligands triphenylphosphine, and one S is from one sulfur-containing ligand thiourea; the molecular structure is shown as formula (I):
the cuprous iodide complex fluorescent sensing material emits weak fluorescence under the excitation of ultraviolet light, and is difficult to observe by naked eyes; after the sensor is placed in a pyridine VOC steam environment, the sensor can quickly show a similar lighting luminous effect, and therefore, the sensor can be used as a sensing material for detecting the pyridine VOC.
2. The method for preparing a cuprous iodide complex fluorescence sensing material according to claim 1, comprising the steps of:
(1) dissolving CuI powder in acetonitrile at room temperature;
(2) dissolving TPP powder in acetonitrile at room temperature;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) dissolving TU powder in acetonitrile at room temperature, adding into the solution A, mixing and stirring to fully perform coordination reaction to obtain a solution B;
(5) filtering the obtained solution B, performing reduced pressure rotary evaporation at room temperature, and drying to obtain crystal powder, namely a target product; the molar ratio CuI to TPP to TU of the three reactants is 1: 2: 1.
3. The application of the paper-based fluorescence sensing film based on the cuprous iodide complex fluorescence sensing material is characterized in that: the fluorescence sensing film is prepared by mixing cuprous iodide complex fluorescence sensing material CuI (TPP)2(TU) dissolving and coating on test paper base paper; the paper-based fluorescent film (or called as fluorescent test paper) can rapidly show a similar lighting luminous effect after being placed in an environment with pyridine VOC steam, shows a stronger lighting response effect when the concentration is higher, shows reversible rapid selective response and sensitively-identified fluorescent sensing performance, and can be used as a portable fluorescent sensing test paper device for convenient detection of pyridine VOC; wherein the structural formula of the cuprous iodide complex fluorescent sensing material is CuI (TPP)2(TU), wherein TPP is triphenylphosphine ligand which is neutral in electricity, TU is thiourea ligand which contains sulfur; the cuprous iodide complex fluorescent sensing material is a triclinic system, a P-1 space group, unit cell parameters of a =9.7713(3) A, b =11.8827(4) A, c =16.0872(6) A, α =85.1850(10) DEG, β =80.3690(10) DEG, γ =69.6340(10) DEG, and V =1725.76(10) A3 , Z=2，DC=1.534 g/cm3 (ii) a The molecular structure of the material is as shown in formula (I):
4. the application of claim 3, wherein the preparation method of the paper-based fluorescence sensing film based on the cuprous iodide complex fluorescence sensing material comprises the following steps:
(1) at room temperatureCopper iodide complex CuI (TPP)2(TU) the powder was dissolved in acetonitrile;
(2) manufacturing a cellulose film into a shape which is required to be conveniently applied to form test paper base paper;
(3) mixing the above complex CuI (TPP) at room temperature2(TU) coating the solution on test paper base paper;
(4) and finally, drying the coated test paper under a vacuum condition, and obtaining the sensing film after drying.
5. The application of the polymer-based doped fluorescent sensing film based on the cuprous iodide complex fluorescent sensing material is characterized in that: the fluorescence sensing film is prepared by mixing cuprous iodide complex fluorescence sensing material CuI (TPP)2(TU) dissolving, doping into polymethyl methacrylate, and coating; after the polymer-based doped fluorescent sensing film is placed in an environment with pyridine VOC steam, the polymer-based doped fluorescent sensing film can quickly show a similar lighting luminous effect, shows a stronger lighting response effect when the concentration is higher, shows the fluorescent sensing performance of quick selective response and sensitive identification, and can be used as a sensitive film in a fluorescent sensor to be applied to the sensing detection of the pyridine VOC; wherein the structural formula of the cuprous iodide complex fluorescent sensing material is CuI (TPP)2(TU), wherein TPP is triphenylphosphine ligand which is neutral in electricity, TU is thiourea ligand which contains sulfur; the cuprous iodide complex fluorescent sensing material is a triclinic system, a P-1 space group, unit cell parameters of a =9.7713(3) A, b =11.8827(4) A, c =16.0872(6) A, α =85.1850(10) DEG, β =80.3690(10) DEG, γ =69.6340(10) DEG, and V =1725.76(10) A3 , Z=2，DC=1.534 g/cm3 (ii) a The molecular structure of the material is as shown in formula (I):
6. the application of claim 5, wherein the preparation method of the polymer-based doped fluorescence sensing film based on the cuprous iodide complex fluorescence sensing material comprises the following steps:
(1) dissolving PMMA solid in dichloromethane at room temperature;
(2) reaction of cuprous iodide Complex CuI (TPP) at room temperature2(TU) the powder was dissolved in acetonitrile;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) and spin-coating the clear solution A on a quartz plate at room temperature, and drying to obtain the sensing film.
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| CN114671855A (en) * | 2022-04-22 | 2022-06-28 | 云南省烟草质量监督检测站 | Acridine ligand for photothermal material, cuprous iodide cluster-based coordination polymer with photo-thermal property, and preparation method and application thereof |
| CN114806547A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Method for preparing CuIP2S type complex fluorescent sensing material by ball milling |
| CN114805840A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Cuprous binuclear cluster luminescent material containing triangular configuration and pyridine fluorescence sensor thereof |
| CN116769159A (en) * | 2023-05-12 | 2023-09-19 | 苏州大学 | Polyarylpyridine and preparation method and application thereof |
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| CN114671855A (en) * | 2022-04-22 | 2022-06-28 | 云南省烟草质量监督检测站 | Acridine ligand for photothermal material, cuprous iodide cluster-based coordination polymer with photo-thermal property, and preparation method and application thereof |
| CN114671855B (en) * | 2022-04-22 | 2024-01-23 | 云南省烟草质量监督检测站 | Acridine ligand for photo-thermal material, cuprous iodide cluster-based coordination polymer with photo-thermal property, and preparation method and application thereof |
| CN114806547A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Method for preparing CuIP2S type complex fluorescent sensing material by ball milling |
| CN114805840A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Cuprous binuclear cluster luminescent material containing triangular configuration and pyridine fluorescence sensor thereof |
| CN116769159A (en) * | 2023-05-12 | 2023-09-19 | 苏州大学 | Polyarylpyridine and preparation method and application thereof |
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